Surface-Pore-Modified N-Doped Amorphous Carbon Nanospheres Tailored with Toluene as Anode Materials for Lithium-Ion Batteries.

The surface modification of amorphous carbon nanospheres (ACNs) through templates has attracted great attention due to its great success in improving the electrochemical properties of lithium storage materials. Herein, a safe methodology with toluene as a soft template is employed to tailor the nanostructure, resulting in ACNs with tunable surface pores. Extensive characterizations through transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption isotherms elucidate the impact of surface pore modifications on the external structure, morphology, and surface area. Electrochemical assessments reveal the enhanced performance of the surface-pore-modified carbon nanospheres, particularly ACNs-100 synthesized with the addition of 100 µL toluene, in terms of the initial discharge capacity, rate performance, and cycling stability. The interesting phenomenon of persistent capacity increase is ascribed to lithium ion movement within the graphite-like interlayer, resulting in ACNs-100 experiencing a capacity upswing from an initial 320 mAh g-1 to a zenith of 655 mAh g-1 over a thousand cycles at a rate of 2 C. The findings in this study highlight the pivotal role of tailored nanostructure engineering in optimizing energy storage materials.

SIRT6-mediated Runx2 downregulation inhibits osteogenic differentiation of human aortic valve interstitial cells in calcific aortic valve disease.

Calcific aortic valve disease (CAVD) is a progressive cardiovascular disorder involving multiple pathogenesis. Effective pharmacological therapies are currently unavailable. Sirtuin6 (SIRT6) has been shown to protect against aortic valve calcification in CAVD. The exact regulatory mechanism of SIRT6 in osteoblastic differentiation remains to be determined, although it inhibits osteogenic differentiation of aortic valve interstitial cells. We demonstrated that SIRT6 was markedly downregulated in calcific human aortic valves. Mechanistically, SIRT6 suppressed osteogenic differentiation in human aortic valve interstitial cells (HAVICs), as confirmed by loss- and gain-of-function experiments. SIRT6 directly interacted with Runx2, decreased Runx2 acetylation levels, and facilitated Runx2 nuclear export to inhibit the osteoblastic phenotype transition of HAVICs. In addition, the AKT signaling pathway acted upstream of SIRT6. Together, these findings elucidate that SIRT6-mediated Runx2 downregulation inhibits aortic valve calcification and provide novel insights into therapeutic strategies for CAVD.

Unveiling Carrier Relaxation Mechanism in Protonated/Deprotonated Carbon Dots and Their Solvent Effects via Ultrafast Spectroscopy.

The intricate nature of the surface structure of carbon dots (CDs) hinders a comprehensive understanding of their emission behavior. In this study, we employ two types of CDs created through acid-alkali treatments, one with surface protonation and the other with surface deprotonation, with the objective of investigating the impact of these surface modifications on carrier behavior using ultrafast spectroscopy techniques. TEM, XRD, FTIR and Raman spectra demonstrate the CDs' structure, featuring graphitic core and abundant surface functional groups. XPS confirms the successful surface modifications of CDs via protonation and deprotonation. Ultrafast transient absorption (TA) spectroscopy reveals that deprotonation modification may decelerate the relaxation process, thereby increasing the visible PL quantum yields (PLQY). Conversely, protonation may accelerate the relaxation process due to the induced low-energy absorption band, resulting in self-absorption and reduced PLQY. Furthermore, TA analysis of CDs in mixed solvents with different proportions of ethanol shows the beneficial effect of ethanol in decelerating the relaxation process, leading to an increased PLQY of 33.7 % for deprotonated CDs and 22.1 % for protonated CDs. This study illuminates the intricate relationship between surface deprotonation/protonation modifications and carrier behavior in CDs, offering a potential avenue for the design of high-brightness CDs for diverse applications.

Impact of Surface Trap States on Electron and Energy Transfer in CdSe Quantum Dots Studied by Femtosecond Transient Absorption Spectroscopy.

The presence of surface trap states (STSs) is one of the key factors to affect the electronic and optical properties of quantum dots (QDs), however, the exact mechanism of how STSs influence QDs remains unclear. Herein, we demonstrated the impact of STSs on electron transfer in CdSe QDs and triplet-triplet energy transfer (TTET) from CdSe to surface acceptor using femtosecond transient absorption spectroscopy. Three types of colloidal CdSe QDs, each containing various degrees of STSs as evidenced by photoluminescence and X-ray photoelectron spectroscopy, were employed. Time-resolved emission and transient absorption spectra revealed that STSs can suppress band-edge emission effectively, resulting in a remarkable decrease in the lifetime of photoelectrons in QDs from 17.1 ns to 4.9 ns. Moreover, the investigation of TTET process revealed that STSs can suppress the generation of triplet exciton and effectively inhibit band-edge emission, leading to a significant decrease in TTET from CdSe QDs to the surface acceptor. This work presented evidence for STSs influence in shaping the optoelectronic properties of QDs, making it a valuable point of reference for understanding and manipulating STSs in diverse QDs-based optoelectronic applications involving electron and energy transfer.

Ruthenium containing molecular electrocatalyst on glassy carbon for electrochemical water splitting.

Electrochemical water splitting constitutes one of the most promising strategies for converting water into hydrogen-based fuels, and this technology is predicted to play a key role in the transition towards a carbon-neutral energy economy. To enable the design of cost-effective electrolysis cells based on this technology, new and more efficient anodes with augmented water splitting activity and stability will be required. Herein, we report an active molecular Ru-based catalyst for electrochemically-driven water oxidation (overpotential of ∼395 mV at pH 7 phosphate buffer) and two simple methods for preparing anodes by attaching this catalyst onto glassy carbon through multi-walled carbon nanotubes to improve stability as well as reactivity. The anodes modified with the molecular catalyst were characterized by a broad toolbox of microscopy and spectroscopy techniques, and interestingly no RuO2 formation was detected during electrocatalysis over 4 h. These results demonstrate that the herein presented strategy can be used to prepare anodes that rival the performance of state-of-the-art metal oxide anodes.

Identification of intermediates of a molecular ruthenium catalyst for water oxidation using in situ electrochemical X-ray absorption spectroscopy.

This is the first study on a Ru(bda) (bda: 2,2'-bipyridine-6,6'-dicarboxylic acid) catalyst in solution using a home-built electrochemical cell, in combination with an energy-dispersive X-ray absorption spectroscopy setup. The oxidation state and coordination number of the catalyst during electrocatalysis could be estimated, while avoiding radiation damage from the X-rays.

An operando X-ray diffraction study of chloroaluminate anion-graphite intercalation in aluminum batteries.

We investigated rechargeable aluminum (Al) batteries composed of an Al negative electrode, a graphite positive electrode, and an ionic liquid (IL) electrolyte at temperatures down to -40 °C. The reversible battery discharge capacity at low temperatures could be superior to that at room temperature. In situ/operando electrochemical and synchrotron X-ray diffraction experiments combined with theoretical modeling revealed stable AlCl4-/graphite intercalation up to stage 3 at low temperatures, whereas intercalation was reversible up to stage 4 at room temperature (RT). The higher-degree anion/graphite intercalation at low temperatures affords rechargeable Al battery with higher discharge voltage (up to 2.5 V, a record for Al battery) and energy density. A remarkable cycle life of >20,000 cycles at a rate of 6C (10 minutes charge time) was achievable for Al battery operating at low temperatures, corresponding to a >50-year battery life if charged/discharged once daily.

Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode.

Recently, interest in aluminium ion batteries with aluminium anodes, graphite cathodes and ionic liquid electrolytes has increased; however, much remains to be done to increase the cathode capacity and to understand details of the anion-graphite intercalation mechanism. Here, an aluminium ion battery cell made using pristine natural graphite flakes achieves a specific capacity of ∼110 mAh g-1 with Coulombic efficiency ∼98%, at a current density of 99 mA g-1 (0.9 C) with clear discharge voltage plateaus (2.25-2.0 V and 1.9-1.5 V). The cell has a capacity of 60 mAh g-1 at 6 C, over 6,000 cycles with Coulombic efficiency ∼ 99%. Raman spectroscopy shows two different intercalation processes involving chloroaluminate anions at the two discharging plateaus, while C-Cl bonding on the surface, or edges of natural graphite, is found using X-ray absorption spectroscopy. Finally, theoretical calculations are employed to investigate the intercalation behaviour of choloraluminate anions in the graphite electrode.

High Coulombic efficiency aluminum-ion battery using an AlCl3-urea ionic liquid analog electrolyte.

In recent years, impressive advances in harvesting renewable energy have led to a pressing demand for the complimentary energy storage technology. Here, a high Coulombic efficiency (∼99.7%) Al battery is developed using earth-abundant aluminum as the anode, graphite as the cathode, and a cheap ionic liquid analog electrolyte made from a mixture of AlCl3 and urea in a 1.3:1 molar ratio. The battery displays discharge voltage plateaus around 1.9 and 1.5 V (average discharge = 1.73 V) and yielded a specific cathode capacity of ∼73 mAh g-1 at a current density of 100 mA g-1 (∼1.4 C). High Coulombic efficiency over a range of charge-discharge rates and stability over ∼150-200 cycles was easily demonstrated. In situ Raman spectroscopy clearly showed chloroaluminate anion intercalation/deintercalation of graphite (positive electrode) during charge-discharge and suggested the formation of a stage 2 graphite intercalation compound when fully charged. Raman spectroscopy and NMR suggested the existence of AlCl4-, Al2Cl7- anions and [AlCl2·(urea)n]+ cations in the AlCl3/urea electrolyte when an excess of AlCl3 was present. Aluminum deposition therefore proceeded through two pathways, one involving Al2Cl7- anions and the other involving [AlCl2·(urea)n]+ cations. This battery is a promising prospect for a future high-performance, low-cost energy storage device.

3D Graphitic Foams Derived from Chloroaluminate Anion Intercalation for Ultrafast Aluminum-Ion Battery.

A 3D graphitic foam vertically aligned graphitic structure and a low density of defects is derived through chloroaluminate anion intercalation of graphite followed by thermal expansion and electrochemical hydrogen evolution. Such aligned graphitic structure affords excellent Al-ion battery characteristics with a discharge capacity of ≈60 mA h g-1 under a high charge and discharge current density of 12 000 mA g-1 over ≈4000 cycles.

Improving the Photocurrent in Quantum-Dot-Sensitized Solar Cells by Employing Alloy PbxCd1-xS Quantum Dots as Photosensitizers.

Ternary alloy PbxCd1-xS quantum dots (QDs) were explored as photosensitizers for quantum-dot-sensitized solar cells (QDSCs). Alloy PbxCd1-xS QDs (Pb0.54Cd0.46S, Pb0.31Cd0.69S, and Pb0.24Cd0.76S) were found to substantially improve the photocurrent of the solar cells compared to the single CdS or PbS QDs. Moreover, it was found that the photocurrent increases and the photovoltage decreases when the ratio of Pb in PbxCd1-xS is increased. Without surface protecting layer deposition, the highest short-circuit current density reaches 20 mA/cm² under simulated AM 1.5 illumination (100 mW/cm²). After an additional CdS coating layer was deposited onto the PbxCd1-xS electrode, the photovoltaic performance further improved, with a photocurrent of 22.6 mA/cm² and an efficiency of 3.2%.

Improved performance of colloidal CdSe quantum dot-sensitized solar cells by hybrid passivation.

A hybrid passivation strategy is employed to modify the surface of colloidal CdSe quantum dots (QDs) for quantum dot-sensitized solar cells (QDSCs), by using mercaptopropionic acid (MPA) and iodide anions through a ligand exchange reaction in solution. This is found to be an effective way to improve the performance of QDSCs based on colloidal QDs. The results show that MPA can increase the coverage of the QDs on TiO2 electrodes and facilitate the hole extraction from the photoxidized QDs, and simultaneously, that the iodide anions can remedy the surface defects of the CdSe QDs and thus reduce the recombination loss in the device. This hybrid passivation treatment leads to a significant enhancement of the power conversion efficiency of the QDSCs by 41%. Furthermore, an optimal ratio of iodide ions to MPA was determined for favorable hybrid passivation; results show that excessive iodine anions are detrimental to the loading of the QDs. This study demonstrates that the improvement in QDSC performance can be realized by using a combination of different functional ligands to passivate the QDs, and that ligand exchange in solution can be an effective approach to introduce different ligands.

Simultaneous multiple wavelength upconversion in a core-shell nanoparticle for enhanced near infrared light harvesting in a dye-sensitized solar cell.

The efficiency of most photovoltaic devices is severely limited by near-infrared (NIR) transmission losses. To alleviate this limitation, a new type of colloidal upconversion nanoparticles (UCNPs), hexagonal core-shell-structured ß-NaYbF4:Er(3+)(2%)/NaYF4:Nd(3+)(30%), is developed and explored in this work as an NIR energy relay material for dye-sensitized solar cells (DSSCs). These UCNPs are able to harvest light energy in multiple NIR regions, and subsequently convert the absorbed energy into visible light where the DSSCs strongly absorb. The NIR-insensitive DSSCs show compelling photocurrent increases through binary upconversion under NIR light illumination either at 785 or 980 nm, substantiating efficient energy relay by these UCNPs. The overall conversion efficiency of the DSSCs was improved with the introduction of UCNPs under simulated AM 1.5 solar irradiation.

Solar cells sensitized with type-II ZnSe-CdS core/shell colloidal quantum dots.

Type-II quantum dots (QDs) were applied for QDs-sensitized solar cells for the first time and showed prominent absorbed photon to current conversion efficiency.

Two novel carbazole dyes for dye-sensitized solar cells with open-circuit voltages up to 1 V based on Br(-)/Br(3)(-) electrolytes.

Dye-sensitized solar cells (DSCs) based on two novel carbazole dyes (TC301 and TC306) and a Br(-)/Br(3)(-) redox mediator in dried CH(3)CN solutions as electrolytes yielded a V(oc) of 1.156 V and a eta value of 3.68% and a V(oc) of 0.939 V and a eta value of 5.22% under simulated AM 1.5, respectively. The dyes TC301 and TC306 have more positive HOMO levels (1.59 and 1.38 V vs NHE) than the redox potential of Br(-)/Br(3)(-)-based electrolytes, which have sufficient driving force to regenerate dyes. Under similar conditions with an I(-)/I(3)(-) instead of a Br(-)/Br(3)(-) redox mediator, DSCs sensitized by the dyes TC301 and TC306 produced a V(oc) of 0.696 V and a eta value of 2.36% and a V(oc) of 0.621 V and a eta value of 4.10%, respectively.